Azinyl organophosphorus compounds

ABSTRACT

Azinyl organophosphorus compounds represented by the following structure: WHEREIN R1 is C1-C4 alkyl, R2 is selected from C1-C4 alkyl optionally substituted by chlorine, bromine or alkoxy, C1-C4 thioalkyl, C6-C10 aryl, C1-C4 alkoxy, phenoxy and thiophenoxy optionally substituted with chlorine, bromine or C1-C3 alkyl; R3 can be hydrogen, C1-C4 alkyl, phenyl optionally substituted with chlorine, bromine or C1-C6 alkyl, C6-C13 aralkyl, and C3-C6 cycloalkyl, X and Y can be O or S, m can be O or 1 and n is an integer ranging from 1 to 3. These compounds have been discovered to possess pesticidal activity, more particularly insecticidal activity.

United States Patent Valint, Jr.

[ 1 May23,1972

[54] AZINYL ORGAN OPHOSPHORUS CONIPOUNDS [72] Inventor: Paul L. Valint,Jr., Woodbridge, NJ.

[73] Assignee: E$o Research and Engineering Company [22] Filed: June 11,1970 [21] Appl. No.: 45,582

[52] U.S. Cl. ..260/239 A, 260/293.73, 260/293.84, 260/293.85, 260/2939,260/3265 A, 260/326.84, 424/200 [51] Int. Cl. ..C07f 9/08, C07f 9/12,CO7f 9/16 [58] Field of Search ..260/239 A, 326.5 A, 294.7 A, 260/2934B, 326.82

[56] References Cited OTHER PUBLICATIONS Petrov et 21., Chem. Abstracts,Vol. 59, C015. 10106- 10107 (1963) Gaertner, J. Org. Chem, Vol. 32,pages 2972- 2976 1967) Primary ExaminerAlton D. Rollins Attorney-Chasanand Sinnock and John Paul Cocoran ABSTRACT Azinyl organophosphoruscompounds represented by the following structure:

x on,

7 Claims, No Drawings AZINYL ORGANOPHOSPHORUS COL/[POUNDS This inventionrelates to derivatives of azinyl ganophosphorus compounds and their useas pesticides.

Many organophosphorus compounds have been found useful in recent yearsas insecticides. Accordingly, it is an object of this invention toprovide new organophosphorus compounds that have outstandinginsecticidal activity.

In accordance with this invention, new organophosphorus compounds havebeen prepared which have the following structural formula:

wherein R is C C alkyl, R is selected from C C alkyl ptionallysubstituted by chlorine, bromine or alkoxy, C -C.

thioalkyl, C C aryl, C,-C., alkoxy, phenoxy and thiophenoxy optionallysubstituted with chlorine, bromine of C C alkyl; R can be hydrogen, C -Calkyl, phenyl optionally substituted with chlorine, bromine or C Calkyl, C -C aralkyl, and C C cycloalkyl, X and Y can be 0 or S, m can be0 or 1 and n is an integer ranging from 1 to 3.

Specific examples included within the above generic formula are asfollows:

Compound l 0,0-dimethyl S-( 1-iso-propylazetidin-3-yl) phosphorothioate2 0,0-diethyl-O-( l-t-butylazetidin-3-yl) phosphate 3 0,0-diethyl-S-(l-t-butylazetidin-3-yl) phosphorothioate 4 0,0-diethyl-S-(l-t-butylazetidin-3-yl) phosphorodithioate 5 0,0-dimethyl-S-(l-t-butylazetidin-B-yl) phosphorodithioate 6 O-ethyl-S-n-propyl-S'-(l-t-butylazetidin-Zi-yl) phosphorodithioate 7 0,0-diethyl-S-(1-cyclohexylazetidin3-yl) phosphorothioate 8 O-ethyl-S- l -propyl Sl-cyclohexylazetidin- 3-yl) phosphorodithioate 9 0,0-dimethyl-S-(l-phenylazetidin-3-yl) phosphorothioate l0 0,0-diethyl-O-(l-benzhydrylazetidin-3-yl) phosphate 1 1 0,0-diethyl'S-(l-benzhydrylazetidin-B-yl) phosphorodithioate l2 0,0-diethyl-S-(l-benzhydrylazetidin-Ii-yl) phosphorothioate l3 0,0-diethyl-S-(l-t-butyl I -oxoazetidin-3-yl) phosphorothioate l40,0-dimethyl-O-pyrrolidin- 3-yl phosphate 15 0,0-dimethyl-S-(l-methylpyrrolidin-Ii-yl) phosphorothioate l6 O-ethyl-S- 1 'propyl S I-phenylpyrrolidin-3- yl) phosphorodithioate l7 0,0-dipropyl-S-(l-chlorophenylpyrrolidin-3- yl) phosphorodithioate l8 0,0-diethyl-S-(l-benzhydrylpyrrolidin-3-yl) phosphorothioate l9 0,0-dimethyl-O-(l-methylpiperidin-3-yl) phosphate 20 0,0-diethyl-S-(l-methylpipen'din-3yl) phosphorothioate 2l 0,0-diethyl-S-(1-methylpiperidin-3-yl) phosphorothioate 22 O-ethyl-S-l-propyl S'-(l-methylpiperidin-3- yl) phosphorodithioate 23 0,0-diethyl-S-( l-methyll-oxopiperidin-3-yl) phosphorothioate 24 0,0-dipropyl-S-(l-phenylpiperidin-3-yl) phosphorodithioate 25 0,0-dimethyl-S-( l-cyclohexylpipen'din-3-yl) phosphorothioate 26 0,0-diethyl-O-(l-benzhydrylpiperidin- 3-yl) phosphate The preparation of theazetidin-3-ol precursors of the claimed compounds has been described byV. R. Gaertner [Tetrahedron Letters, 4691 (1966); J. Org. Chem., 32,2972 The 3-hydroxy compounds can be converted to phosphate esters byreaction with a phosphorochloridate in the presence of an acid bindingagent (B) according to the following schematic equation:

In this reaction, the phosphorochloridate and acid binding agent, i.e.pyridine, triethyl amine, etc., are employed in equivalent amounts inthe presence of an aprotic solvent such as diethyl ether, benzene orchloroform. The reaction temperature can very between 20 and 125 C.,preferably between 25 and C. The pressure employed is usuallyatmospheric. The reaction times can vary from 1 hour to 24 hours,preferably 2 to 8 hours.

In order to prepare derivatives in which the azinyl moiety is attachedto the phosphorus atom through a sulfur atom, the 3- hydroxy compoundscan be converted to readily displaceable groups, such as tosylate orbromide. The resulting compounds can then be reacted withphosphorothioate salts to give rise to the desired esters.

1. NaH

(Reaction B) (Reaction (J) Reaction A:

In this reaction, the phosphorus tribromide is employed in excess in thepresence of an aprotic solvent such as diethyl ether, benzene, orchloroform. The reaction temperature can vary from 20 to 100 C.,preferably between 25 and 80 C. The pressure employed is usuallyatmospheric. The reaction times can vary from 4 hours to 48 hours,preferably 10 hours to 20 hours. The desired product is isolated forfurther reaction to yield phosphate esters.

Reaction B:

In this reaction, sodium hydride is employed in excess in the presenceof an aprotic solvent such as diethyl ether, benzene or toluene. Thereaction temperature can vary between 20 and 40 C., preferably 5 and 25C. The pressure employed is usually atmospheric. An equivalent amount ofp-toluenesulfonyl chloride is utilized under similar solvent,temperature and pressure conditions. The reaction times can vary from 2hours to 24 hours, preferably from 4 to 8 hours. The desired product isisolated for further reaction to yield phosphate esters.

In the conversion of the 3-bromo or 3-tosyl azinyl compounds tophosphorotioate esters, stoichiometric amounts of reactants areutilized. The displacement reaction can be carried out with or without asolvent. However, it is usually advantageous to use a solvent which canbe a polar organic compound such as nitriles, ketones, alcohols, etc.Hydrocarbons and their chlorinated derivatives such as xylenes,chlorobenzene, etc. are also suitable. The preferred solvents for thisdisplacement reaction are either acetonitrile or methanol.

The reaction temperatures can vary from about to 150 C. preferably fromabout 25 to 120 C. The pressure of the reactions is usually atmospheric.

Reaction times can vary from 1 to 48 hours, preferably from 2 to 12hours.

Reaction C:

The N-oxide derivative can be prepared easily by the oxidation of thefinal organophosphates with oxidizing reagents such as peracids andhydrogen peroxide, etc. In this reaction equivalent amounts of thereactants are employed preferably in the presence of solvent such aschloroform, methylene chloride, etc., the temperature of the reactioncan vary from to 70 C., preferably between 0 to 50 C. The reaction timecan be from to 80 hours, preferably from 24-50 hours.

Insecticidal compositions of the invention are prepared by admixing oneor more of the active ingredients defined heretofore, in insecticidallyeffective amounts with a conditioning agent of the kind used andreferred to in the art as a pest control adjuvant or modifier to provideformulations adapted for ready and efficient application to soil orweeds (i.e., unwanted plants) using conventional applicator equipment.

Thus, the insecticidal compositions or formulations are prepared in theform of solids or liquids. Solid compositions are preferably in the formof granulars or dusts.

The compositions can be compounded to give homogeneous free-flowingdusts by admixing the active compound or compounds with finely dividedsolids preferably talc, natural clays, pyrophyllite, diatomaceous earth,or flours such as walnut shell, wheat, redwood, soya bean, andcottonseed flours. Other inert solid conditioning agents or carriers ofthe kind conventionally employed in preparing pest control compositionsin powdered form can be used.

Granulars can be compounded by absorbing the compound in liquid formonto a preformed granular diluent. Such diluents as natural clays,pyrophyllite, diatomaceous earth, flours such as walnut shell, as wellas granular sand can be employed.

In addition, granulars can also be compounded by admixing the activeingredient with one of the powdered diluents described hereinabove,followed by the step of either pelleting or extruding the mixture.

Liquid compositions of the invention are prepared in the usual way byadmixing one or more of the active ingredients with a suitable liquiddiluent medium. In the case where the compounds are liquids, they may besprayed in ultra low volume as such. With certain solvents, such asalkylated naphthalene or other aromatic petroleum solvents, dimethylformamide, cycloketone, relatively high up to about 50 percent by weightor more concentration of the active ingredient can be obtained insolution.

The insecticidal compositions of the invention whether in the form ofdusts or liquids, preferably also include a surface active agentsometimes referred to in the art as a wetting, dispersing, oremulsifying agent. These agents, which will be referred to hereinaftermore simply as surface-active dispersing agents, cause the compositionsto be easily dispersed in water to give aqueous sprays which, for themost part, constitute a desirable composition for application.

The surface-active dispersing agents employed can be of the anionic,cationic, or nonionic type and include, for example, sodium andpotassium oleate, the amine salts of oleic acid, such as morpholine anddimethylamine oleates, the sulfonated animal and vegetable oils, such assulfonated fish and castor oils, sulfonated petroleum oils, sulfonatedacyclic hydrocan bons, sodium salt of lignin sulfonic acid (goulac),alkylnaphthalene sodium sulfonate, sodium salts of sulfonatedcondensation products of naphthalene and formaldehyde, sodium laurylsulfate, disodium monolauryl phosphate, sorbitol laurate,pentaerythritol monostearate, glycerol monostearate, diglycol oleate,polyethylene oxides, ethylene oxide condensation products with stearylalcohol and alkylphenol, polyvinyl alcohols, salts, such as the acetateof polyamines from reductive amination of ethylene/carbon monoxidepolymers, laurylamine hydrochloride, lauryl pyridinium bromide, stearyltrimethylammonium bromide, cetyldimethylbenzyl ammonium chloride,lauryldimethylamine oxide, and the like. Generally, the surface-activeagent will not comprise more than about 5 to 15 percent by weight of thecomposition, and in certain compositions the percentage will be 1% orless. Usually, the minimum lower concentration will be 0. 1%.

The active compound is, of course, applied in an amount suflicient toexert the desired insecticidal action.

Fertilizer materials, herbicidal agents, and other pest control agentssuch as insecticides and fungicides can be included in the insecticidalcompositions of the invention if desired.

The term carrier or diluent as used herein means a material, which canbe inorganic or organic and synthetic or of natural origin, with whichthe active ingredient is mixed or formulated to facilitate its storage,transport, and handling and application to the plants to be treated. Thecarrier is preferably biologically and chemically inert and, as used,can be a solid or fluid. When solid carriers are used, they arepreferably particulate, granular, or pelleted; however, other shapes andsizes of solid carrier can be employed as well. Such preferably solidcarriers can be natural occurring mineralsalthough subsequentlysubjected to grinding, sieving, purification, and/or othertreatmentsincluding, for example, gypsum; tripolite; diatomaceous earth;mineral silicates such as mica, vermiculite, talc, and pyrophyllite;clays of the montmorillonite, kaolinite, or attapulgite groups; calciumor magnesium limes, or calcite and dolomite; etc. Carriers producedsynthetically, as for example, synthetic hydrated silica oxides andsynthetic calcium silicates can also be used, and many proprietaryproducts of this type are available commercially. The carrier can alsobe an elemental substance such as sulfur, or carbon, preferably anactivated carbon. If the carrier possesses intrinsic catalytic activitysuch that it would decompose the active ingredient, it is advantageousto incorporate a stabilizing agent, as for example, polyglycols such asdiethylene glycol, to neutralize this activity and thereby preventpossible decomposition of the present compounds.

For some purposes, a resinous or waxy carrier can be used, preferablyone which is solvent soluble or thermoplastic, including fusiblematerials. Examples of such carriers are natural or synthetic resinssuch as a coumarone resin, rosin, copal, shellac, dammar, polyvinylchloride, styrene polymers and copolymers, a solid grade ofpolychlorophenol such as is available under the registered trademarkAroclor," a bitumen, an asphaltite, a wax for example, beeswax or amineral wax such as paraffin wax or montan wax, or a chlorinated mineralwax, or a microcrystalline wax such as those available under theregistered trademark Mikrovan Wax. Compositions comprising such resinousor waxy carriers are preferably in granular or pelleted form.

Fluid carriers can be liquids, as for example, water, or an organicfluid, including a liquefied normally vaporous or gaseous material, or avaporous or gaseous material, and can be solvents or nonsolvents for theactive material. For example, the horticultural petroleumspray oilsboiling in the range of from about 275 to about 575 F., or boiling inthe range of about 575 to about 1,000 F. and having an unsulfonatableresidue of at least about 75 percent and preferably of at least about 90percent, or mixtures of these two types of oil, are particularlysuitable liquid carriers.

The carrier can be mixed or formulated with the active material duringits manufacture or at any stage subsequently. The carrier can be mixedor formulated with the active material in any proportion depending onthe nature of the carrier. One or more carriers, moreover, can be usedin combination.

The compositions of this invention can be concentrates, suitable forstorage or transport and containing, for example, from about 5 to about90 percent by weight of the active ingredient, preferably from about toabout 80 wt. percent. These concentrates can be diluted with the same ordifferent carrier to a concentration suitable for application. Thecompositions of this invention may also be dilute compositions suitablefor application. In general, concentrations of about 0.1 to about 10percent by weight, of active material based on the total weight of thecomposition are satisfactory, although lower and higher concentrationscan be applied if necessary.

The compositions of this invention can also be formulated as dusts.These comprise an intimate admixture of the active ingredient and afinely powdered solid carrier such as aforedescribed. The powderedcarriers can be oil-treated to improve adhesion to the surface to whichthey are applied. These dusts can be concentrates, in which case ahighly sorptive carrier is preferably used. These require dilution withthe same or a different finely powdered carrier, which can be of lowersorptive capacity, to a concentration suitable for application.

The compositions of the invention can be formulated as wettable powderscomprising a major proportion of the active ingredient mixed with adispersing, i.e., deflocculating or suspending agent, and if desired, afinely divided solid carrier and/or a wetting agent. The activeingredient can be in particulate form or adsorbed on the carrier andpreferably constitutes at least about 10 percent, more preferably atleast about percent, by weight of the composition. The concentration ofthe dispersing agent should in general be between about 0.5 and about 5percent by weight of the total composition, although larger or smalleramounts can be used if desired.

The dispersing agent used in the composition of this invention can beany substance having definite dispersing, i.e., deflocculating orsuspending, properties as distinct from wetting properties, althoughthese substances can also possess wetting properties as well.

The dispersant or dispersing agent used can be protective colloids suchas gelatin, glue, casein, gums, or a synthetic polymeric material suchas polyvinyl alcohol and methyl cellulose. Preferably, however, thedispersants or dispersing agents used are sodium or calcium salts ofhigh molecular weight sulfonic acids, as for example, the sodium orcalcium salts of lignin sulfonic acids derived from sulfite cellulosewaste liquors. The calcium or sodium salts of condensed aryl sulfonicacid, for example, the products known as Tamol 731, are also suitable.

The wetting agents used can be nonionic type surfactants, as

' for example, the condensation products of fatty acids containing atleast 12, preferably 16 to 20, carbon atoms in the molecule, or abieticacid or naphthenic acid obtained in the refining of petroleumlubricating oil fractions with alkylene oxides such as ethylene oxide orpropylene oxide, or with both ethylene oxide and propylene oxide, as forexample, the condensation product of oleic acid and ethylene oxidecontaining about six to 15 ethylene oxide units in the molecule. Othernonionic wetting agents like polyalkylene oxide polymers, commerciallyknown as Pluronics can be used. Partial esters of the above acids withpolyhydric alcohols such as glycerol, polyglycerol, sorbitol, ormannitol can also be made.

Suitable anionic wetting agents include the alkali metal salts,preferably sodium salts, of sulfuric acid esters or sulfonic acidscontaining at least 10 atoms in a molecule, for example, the sodiumsecondary alkyl sulfates, dialkyl sodium sulfosuccinate available underthe registered trademark Teepol," sodium salts of sulfonated castor oil,sodium dodecyl benzene sulfonate.

Granulated or pelleted compositions comprising a suitable carrier havingthe active ingredient incorporated therein are also included in thisinvention. These can be prepared by impregnating a granular carrier witha solution of the inert ingredient or by granulating a mixture of afinely divided solid carrier and the active ingredient. The carrier usedcan consist of or contain a fertilizer or fertilizer mixture, as forexample, a superphosphate.

The compositions of this invention can also be formulated as solutionsof the active ingredient in an organic solvent or mixture of solvents,such as for example, alcohols; ketones, especially acetone; ethers;hydrocarbons; etc.

Where the toxicant itself is a liquid these materials can be sprayed oncrops or insects without further dilution.

Petroleum hydrocarbon fractions used as solvents should preferably havea flash point above 73 F., an example of this being a refined aromaticextract of kerosene. Auxiliary solvents such as alcohols, ketones, andpolyalkylene glycol ethers and esters can be used in conjunction withthese petroleum solvents.

Compositions of the present invention can also be formulated asemulsifiable concentrates which are concentrated solutions or dispersionof the active ingredient in an organic liquid, preferably awater-insoluble organic liquid, containing an added emulsifying agent.These concentrates can also contain a proportion of water, for example,up to about 50 percent by volume, based on the total composition, tofacilitate subsequent dilution with water. Suitable organic liquidsinclude, e.g., the above petroleum hydrocarbon fractions previouslydescribed.

The emulsifying agent can be of the type producing waterin-oil typeemulsions which are suitable for application by low volume spraying, oran emulsifier of the type producing oil-inwater emulsions can be used,producing concentrates which can be diluted with relatively largevolumes of water for application by high volume spraying or relativelysmall volumes of water for low volume spraying. in such emulsions, theactive ingredient is preferably in a nonaqueous phase.

The present invention is further illustrated in greater detail by thefollowing examples, but it is to be understood that the presentinvention in its broadest aspects, is not necessarily limited in termsof the reactants, or specific temperatures, residence times, separationtechniques and other process conditions, etc.; or dosage level, exposuretimes, test plants used, etc. by which the compounds and/or compositionsdescribed and claimed are prepared and/or used.

Example l-Preparation of l-t-Butylazetidin-3-ol A mixture of 277.5 g.(3.0 moles) of epichlorohydrin and 219 g. (3 moles) of2-a.rnino-2-methyl propane in 1,200 ml. of methanol was stirred atambient temperature for 48 hours. The reaction mixture was heated to 60C. for 72 hours and the methanol was removed under vacuum. The solidresidue was basified with 50 percent sodium hydroxide solution andextracted with 2 liters of ether. The ether extracts were dried oversodium hydroxide pellets and the ether was removed under vacuum. Theviscous residue was distilled under vacuum to yield 120.5 g. (31percent) of product as shown by nuclear magnetic resonance (nmr)spectroscopy.

Analyses:Cald for C H, NO: C,65.1; 11,1 1.6; N,10.8.

Example 2Preparation of l-t-Butylazetidin-3-yl-Tosylate Sodium hydride(11.8 g., 0.3 mole based on 61 percent in mineral oil) was washed with 3X 150 ml. of hexane and suspended in 250 ml. of benzene.1-t-Butyl-azetidin-3-ol (20.0 g., 0.155 mole) was added portionwise andthe mixture was cooled to C. p-Toluene sulfonyl chloride (24.0 g., 0.16mole) was added over a 2-hour period and left to stir at ambienttemperature for three hours. The excess NaI-I was destroyed cautiouslyby the dropwise addition of water. The mixture was then washed with 3 X200 ml. of water, the benzene layer was dried over MgSQ, and the benzenewas removed under vacuum. The residue crystallized on standing to give30 g. (70 percent) of product. Recrystallized from hexane, mp. 69.570 C.

Found: C,59.5; I-1,7.34; N,4.82 Example 3Preparation of 0,0'-Diethyltylazetidin-3-yl)phosphate 1-t-Butylazetidin-3-ol (12.9 g., 0.1 mole)and 17.2 g. (0.1 mole) of 0,0-diethyl phosphorochloridate were dissolvedin 100 ml. of benzene and 10.1 g. (0.1 mole) of triethylamine were addeddropwise. The reaction temperature rose to 35 C. and a white solidprecipitated. The mixture was stirred at ambient temperature for 18hours and the solid was removed by filtration. The filtrate was washedwith percent aqueous NaI-ICO dried over MgSO and solvent was removedunder vacuum to yield 14.8 g. (56 percent) of desired product as shownby nmr spectroscopy.

Anal; Calcd. for C H NOJ: C,50.0; H,8,96; P,11.5.

Found: C,46.4; 11,8.76', P, 1 2.4 Example 4Preparation of 0,0-DiethylS-( l-t-butylazetidin- 3-yl) phosphorothioate 1-t-Butylazetidin-3-yltosylate 14.0 g., 0.06 mole) and 15.3 g. (0.08 mole) of ammonium0,0-diethyl phosphorothioate were dissolved in 250 ml. of methanol andheated to reflux for 25 hours. The methanol was removed under vacuum,the residue was dissolved in chloroform and washed with 100 ml. of H 0and 100 m]. of 5% NaHCO The chloroform solution was dried over MgSO. andchloroform was removed under vacuum to yield 14. lg. (84 percent) of thedesired product as shown by nmr spectroscopy.

Anal.: Calcd. for C H NO PS:C,47.0;l-1,8.54; P11.03.

Found: C,43.0; 14,8.53; P,1 1.0. Example 5-Preparation of 0,0-Diethyltylazetidin-3-yl) phosphorodithioate According to the procedure ofExample 4, 14.2 g. (0.05 mole) of l-t-butylazetidin-3-yl tosylate and16.2 g. (0.08 mole) of ammonium 0,0-diethyl phosphorodithioate werereacted to yield 9 g. (61 percent) of the desired product as shown bynmr spectroscopy.

AnaL'. Cal'd. for C i-l NO PS z 11.7.68; N,4.48; S,20.2

Found: H770; N,4.96;S,21.7. Example 6Preparation of tylazetidin-3-y1)phosphorodithioate According to the procedure of Example 4, 14.2 g.(0.05 mole) of l-t-butylazetidin-3-yl tosylate and 10.8 g. (0.055 mole)of 0,0-dimethyl phosphorodithioate were reacted to yield 10.2 g. (76percent) of the desired product as shown by nmr spectroscopy.

Anal.: Cald. for C l-I ONO PS C,40.2; H,7.43; N,5.20;

Found: C,40.7; H,7.60; N,5.1; P, 10.5 Example 7Preparation of O-EthylS-l-propyl S'-(l-t-buty1azetidin-3-yl) Phosphorodithioate According tothe procedure of Example 4, 42.5 g. (0.15 mole) ofl-t-butylazetidin-3-yl tosylate and 43.1 g. (0.15 mole) of ethyltrimethyl ammonium O-ethyl S-l-propyl phosphorodithioate were reacted toyield 27.4 g. (59 percent) of the desired product as shown by nmrspectroscopy.

Anal.: Calcd for C H NO PS C,46.3; I-I,8.36; N,4.50;

Found: C,45.5;l-1,8.77;N,4.19; 1 .9.99.

Example 8Preparation of 1Cyclohexylazetidin-3-ol According to theprocedure of Example 1, 250 g. (2.52 moles) of cyclohexylamine and 183.1g. (2.52 moles) of eqichlorohydrin were reacted to yield 52.5 g. (13percent) of desired product as shown by nmr spectroscopy.

Found: C,69.8; H,10.8; N,9.28. epichlorohydrin Example 9Preparation of1-Cyclohexylazetidin-3-yl Tosylate According to the procedure of Example2,766 g. (0.4 mole) of 1cyclohexylazetidin-3-ol 43.2g. (1.6 moles) ofsodium hydride and 76.2 g. (0.4 moles) of p-toluene sulfonyl chloridewere reacted to yield 39 g. (32 percent) of the desired product as shownby nmr spectroscopy. Example l0-Preparation of0,0Diethyl(1-cyclohexylazetidin-3-yl) phosphorothioate According to theprocedure of Example 4, 7.7 g. (0.025 mole) of l-cyclohexylazetidin-3-yltosylate and 7.5 g. (0.04 mole) of ammonium 0,0-diethyl phosphorothioatewere reacted in acetonitrile to yield 2.4 g. of desired product as shownby nmr spectroscopy.

AnaL: Calcd. for C13H2BNO3PS: C,50.8, l-l,8.47; P, 10.1.

Found: C,49.3; H,8.82; P,9.89. Example 11-Preparation of 0,0-Diethyl S-(l-Benzhydrylazetidin-3-yl) Phosphorodithioate According to the procedureof Example 4, 9.05 g. (0.25 mole) of l-benzhydrylazetidin-3-yl tosylateand 7.5 g. (0.04 Mole) of ammonium 0,0-diethyl phosphorothioate werereacted to give 8.2 g. (84 percent) of the desired product as shown bynmr spectroscopy.

Anal: Calcd. for C H NO PS: C,61.4; 1-I,6.65; N,3.59;

Found: C,62.7; I-I,7.03; N,3.96; P,7.32. Example 12Preparation of3-Bromo-l-Methylpiperidine 3-I-[ydroxy-1-Methylpiperidine (41.4 g., 0.36mole) was dissolved in 600 ml. of benzene and 42 ml. of phosphorustribromide were added dropwise. The reaction mixture was heated toreflux for 2 hours. A 25 percent aqueous solution of NaOH (500 ml.) wasadded to reaction mixture. The benzene layer was dried over MgSO andbenzene was removed under vacuum to yield 24.8g. (39 percent) of desiredproduct as shown by nmr spectroscopy. Example l3-Preparation of0,0-Diethyl piperidine-3-yl) Phosphorothioate According to procedure ofExample 4, 14.4 g. (0.082 mole) of 3-bromo-l-methylpiperidine and 15.3g. (0.082 mole) of ammonium 0,0-diethyl phosphorothioate were reacted toyield 13.4 g. (51 percent) of 83 percent pure (glc) desired product asshown by nmr spectroscopy. Example l4Preparation of 0,0-Diethylpiperidine-3-yl) Phosphorodithioate According to the procedure ofExample 4, 14.4g. (0.082 mole) of 3-bromo-l-methylpiperidine and 17.0g., (0.082 mole) of ammonium 0,0-diethyl phosphorodithioate were reactedto give 15.5 g. (48 percent of 72 percent pure (glc) desired product asshown by nmr spectroscopy. Example 15Preparation of O-Ethyl S-l-PropylS-( 1- Methylpiperidine-3-yl) Phosphorodithioate According to theprocedure of Example 4, 12.6 g. (0.07 mole) of3-bromo-l-methylpiperidine and 16.7 g. (0.07 mole) of potassium O-ethylS-l-propyl phosphorodithioate were reacted to yield 13.2 g. (35 percent)of desired product as shown by nmr spectroscopy. Example l6-Preparationof 0,0-Diethyl (l-Methyl-l-oxopiperidine-3-yl) Phosphorothioate0,0-Diethyl (l-Methylpiperidine-3-yl) phosphorothioate (3.2 g. 0.012mole) was dissolved in ml. of ClICl and 2.3 g. (0.012 mole) ofm-chloroperbenzoic acid in 100 ml. of CI-ICl were added. The resultingmixture was stirred at ambient temperature for 48 hr. The solution waswashed with 5%Na1-1C0 until neutral (pl-i=7), dried over MgSO, and CHClremoved under vacuum to yield 1.2 g. (42 percent) of the desired productas shown by nmr spectroscopy.

(l-methyll-Methyl- GENERAL EXPERIMENTAL PROCEDURES FOR BIOLOGICALTESTING [n the examples which follow, the new azinyl thiophosphateesters were treated in the greenhouse and in the laboratory to determinetheir biological activity.

The experimental compounds were tested as aqueous emulsions. Theseemulsions were prepared by dissolving the compound in acetone anddispersing it in distilled water with Triton X-lOO, an alkylarylpolyether alcohol derived by the reaction of i-cetyl phenol withethylene oxide, to give spray emulsions containing the desiredconcentration of the compound. These emulsions were then used instandard laboratory tests described below.

Mexican Bean Beetle: Bean leaves were dipped in the emulsion of the testchemical and allowed to dry. The individual treated leaves were placedin Petri dishes and five Mexican bean bettle larvae introduced into eachof the two replicate dishes.

Mites, Contact: Potted bean plants infested with the twospotted spidermites were placed on a turntable and sprayed with a formulation of thetest chemical. The plants were held for seven days and the degree ofmite control was rated after this period.

Mites, Systemic: Bean plants were treated by applying 20 ml. of theformulated test chemical to the soil. The mites were transferred to theplants after 24 hours. The plants were held for seven more days and thedegree of mite control rated. Aphid, Contact: Potted nasturtium plantsinfested with the bean aphids were placed on a turntable and sprayedwith a formulation of the test chemical. The plants were held for twodays and the degree of aphid control was rated.

Aphid, systemic: Nasturtium plants were treated by applying 20 ml. ofthe formulated test chemical to the soil. The aphids were transferred tothe plants after 24 hours. The plants were held for 48 additional hoursand the degree of the Aphid control rated.

Southern Army Worm: Bean leaves were dipped in the emulsion of the testchemical of desired concentration and allowed to dry. The individualtreated leaves were placed in petri dishes and five Southern Army larvaeintroduced into each of the two replicate dishes. The plants were heldfor 2 days and the degree of control was rated.

Some of the compounds were also tested against other species ofcoleoptera such as confused flour beetle and spider beetle, as well asadult Mexican bean beetles. They were also tested for theirefiectiveness to control German cockroaches. Tests were also done todetermine their ovicidal action. The compounds were ground active in oneor more of these tests What is claimed is:

1. Compounds of the formula wherein R is C,C, alkyl; R is C C. alkyl, C-C, alkoxy, or C C alkylthio; R is t-butyl or cyclohexyl; and each of Xand Y is oxygen or sulfur.

2. A compound according to claim 1 which is, 0,0-Diethyl- O-(l-t-butylazetidin-3-yl) phosphate.

3. A compound according to claim 1, which is, 0,0-Diethyl- S-(l-t-butylazetidin-3-yl) phosphorothioate.

4. A compound according to claim 1 which is, 0,0-Diethyl S-(l-t-butylazetidin-3-yl) phosphorodithioate.

5. A compound according to claim 1, which is 0,0- Dimethyl S-(l-t-butylazetidin-Il-yl) phosphorodithioate.

6. A compound according to claim 1, which is O-Ethyl S-npropyl S-(l-t-butylazetidin-S-yl) phosphorodithioate.

7. A compound according to claim 1, which is 0,0-Diethyl S-(1-cyclohexylazetidin-3-yl)phosphorothioate.

TABLE I.INSECTICIDAL ACTIVITY OF ORGANOPHOSPHAIE DERIVATIVES OFl-ALKYLAZETIDIN-Zi-OLS Percent mortality Mexican Mites Aphids Cone beanS. army Experimental compounds (ppm beetle worm Contact Systemic ContactSystemic 0,0 di0thyl O-(l-tbutylazetidinQ-yl) phosphate 28 0 4 A 0 uQo-dicthyl S-(Lbbutylazetidin-3-yl) phosphorothioate 28 g 0.0- ii0thylS-(l-t-butylazetidin-3yl) pliosphororlithioate g? g? g 0.0-dinwthylS-(1-t-butylazotidin-B-yl) phosphorodithicate 2g g 7 8 O-ethyl Sl-propylS-(l-t-liutyLnzctidin-Ii-yl) phosphorodithioate ,8 1%? lgg 8 oodmh i(Leyclohoxylazctidin-S-yl) phosphorotliioate 28 8 gg 0,0-(iieth3'lS-(1-benzhydrylazetidin-S-yl) phosphorothioate 28 98 g *Conc.=l00 p.p.m.d 7 7 7 TABLE II.INSECTICIDAL ACTIVITY OF ORGANOPHOSPHATE DERIVATIVES OFl-ME'IHYLPIPERIDINES Percent mortality Mexican Mites Aphids Cone. beanS. army Experimental compounds (p.p.m.) beetle worm Contact SystemicContact Systemic Qo-d ethyl (1-methylpiperidin 3yl) phosphorothioate 2gg 4 7 i 250 20 V 85 95 ,0-d1@ hl(1methylp1pend1n-8-yl)phosphoiodithioate 50 5 7 35 90 O-ethyl -l-propylS-(l-methylpiperidin-B-yl)phosphorodithioate.g 28 188 2 1% 0,0-dit thyl(l-methyl l-oxopiperidin-B-yl) phosphorot' ioate 28 32 S8

2. A compound according to claim 1 which is,O,O-Diethyl-O-(1-t-butylazetidin-3-yl) phosphate.
 3. A compoundaccording to claim 1, which is, O,O-Diethyl-S-(1-t-butylazetidin-3-yl)phosphorothioate.
 4. A compound according to claim 1 which is,O,O-Diethyl S-(1-t-butylazetidin-3-yl) phosphorodithioate.
 5. A compoundaccording to claim 1, which is O,O-Dimethyl S-(1-t-butylazetidin-3-yl)phosphorodithioate.
 6. A compound according to claim 1, which is O-EthylS-n-propyl S''-(1-t-butylazetidin-3-yl) phosphorodithioate.
 7. Acompound according to claim 1, which is O,O-DiethylS-(1-cyclohexylazetidin-3-yl)phosphorothioate.